Nitrogen and dioxolane-containing hydrofluoroethers and methods of using the same

ABSTRACT

Described herein is dioxolane-containing compound of formula (I) wherein (i) Rf 1  and Rf 2  are independently linear or branched perfluoroalkyi groups having with 1-8 carbon atoms and optionally comprise at least one catenated heteroatom, or (ii) Rf 1  and Rf 2  are bonded together to form a ring structure having 4-6 carbon atoms and optionally comprise one or more catenated heteroatoms; Rf 2  is a linear or branched perfluoroalkyi groups having with 1-3 carbon atoms; and R 4  and R 5  are independently selected from H, F, Cl, a linear or branched alkyl group having 1-3 carbon atoms, optionally wherein the alkyl group comprises at least one of: fluorine, chlorine, a hydroxyl group, or a catenated heteroatom; for use in cleaning compositions, as an electrolyte solvent, as a heat transfer fluid, or a vapor phase soldering fluid. There is also provided a method of making the dioxolane-containing compound, comprising: contacting a 1,2-diol compound with a fluorinated ethylenically unsaturated compound in the presence of a base.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage filing under 35 U.S.C. 371 ofPCT/US2017/047879, filed Aug. 22, 2017, which claims the benefit of U.S.Application No. 62/380,617, filed Aug. 29, 2016.

TECHNICAL FIELD

The present disclosure relates to hydrofluoroethers containing dioxolaneand amine moieties, and methods of using the same.

SUMMARY

There continues to be a need for inert fluorinated fluids which have lowglobal warming potential while providing high thermal stability, lowtoxicity, nonflammability, good solvency, and a wide operatingtemperature range to meet the requirements of various applications.Those applications include, but are not restricted to, heat transfer,solvent cleaning, fire extinguishing agents, and electrolyte solventsand additives.

In one aspect, a dioxolane-containing compound of formula (I) isdescribed:

wherein (i) R_(f) ¹ and R_(f) ² are independently linear or branchedperfluoroalkyl groups having with 1-8 carbon atoms and optionallycomprise at least one catenated heteroatom, or (ii) R_(f) ¹ and R_(f) ²are bonded together to form a ring structure having 4-6 carbon atoms andoptionally comprise one or more catenated heteroatoms;R_(f) ³ is a linear or branched perfluoroalkyl groups having with 1-3carbon atoms; andR⁴ and R⁵ are independently selected from H, F, Cl, a linear or branchedalkyl group having 1-3 carbon atoms, optionally wherein the alkyl groupcomprises at least one of: fluorine, chlorine, a hydroxyl group, or acatenated heteroatom.

In one aspect, a working fluid is described comprising thedioxolane-containing compound of formula (I) described above.

In another aspect, an apparatus for heat transfer is describedcomprising the dioxolane-containing compound of formula (I) describedabove,

The above summary is not intended to describe each embodiment. Thedetails of one or more embodiments of the invention are also set forthin the description below. Other features, objects, and advantages willbe apparent from the description and from the claims.

DETAILED DESCRIPTION

As used herein, the term

“a”, “an”, and “the” are used interchangeably and mean one or more; and

“and/or” is used to indicate one or both stated cases may occur, forexample A and/or B includes, (A and B) and (A or B);

“alkyl” refers to a monovalent group that is a radical of an alkane,which is a saturated hydrocarbon. The alkyl group can be linear,branched, cyclic or combinations thereof;

“catenated” means an atom other than carbon (for example, oxygen ornitrogen) that is bonded to at least two carbon atoms in a carbon chain(linear or branched or within a ring) so as to form acarbon-heteroatom-carbon linkage; and

“perfluorinated” means a group or a compound wherein all hydrogen atomsin the C—H bonds have been replaced by C—F bonds.

As used herein, a chemical structure that depicts the letter “F” in thecenter of a ring indicates that all unmarked bonds of the ring arefluorine atoms.

It should be understood, that although not shown, there are hydrogenatoms bonded to the carbon atoms of the cyclic ring to complete thevalency of the individual carbon atoms, as is common nomenclature.

Also herein, recitation of ranges by endpoints includes all numberssubsumed within that range (e.g., 1 to 10 includes 1.4, 1.9, 2.33, 5.75,9.98, etc.).

Also herein, recitation of “at least one” includes all numbers of oneand greater (e.g., at least 2, at least 4, at least 6, at least 8, atleast 10, at least 25, at least 50, at least 100, etc.).

WO Publ. No. 2016/048808 (Lamanna et al.) describes nitrogen-containinghydrofluoroether compounds which can be used in a variety ofapplications. WO Publ. No. 2016/048808 describes a method of making suchcompounds, wherein the additional of a diol to a perfluorinated vinylamine (i.e., N(Rf₁)(Rf₂)-CF═CF₂) in the presence of a base results inthe dimerization of the perfluorinated vinyl amine as shown in Examples10, 16, 18, 25-27 and 30. Surprisingly, in the present disclosure it hasbeen discovered that by reacting a 1,2-diol with a perfluorinated1-alkyl amine in the presence of a base results, not in a dimerizationof the amine compound, but instead a dioxolane-containing amine compoundas illustrated in Scheme 1.

In one embodiment, the compounds of the present disclosure can bereadily prepared in high yield via low cost starting materials. Thestarting materials can be readily purchased or derived fromelectrochemical fluorination. Thus, the compounds described in thepresent disclosure represent a new class of useful and potentially lowcost fluorinated fluids that offer potential advantages in a variety ofapplications including heat transfer, cleaning, and electrolyteapplications.

The dioxolane-containing compounds of the present disclosure (hereinreferred to interchangeably as a compound of the present disclosure) areof the general formula (I)

wherein (i) R_(f) ¹ and R_(f) ² are independently linear or branchedperfluoroalkyl groups having with 1-8 carbon atoms and optionallycomprise at least one catenated heteroatom such as an O, N, or S, or(ii) R_(f) ¹ and R_(f) ² are bonded together to form a fluorinated ringstructure having 4-6 carbon atoms and optionally comprise one or morecatenated heteroatoms;R_(f) ³ is a linear or branched perfluoroalkyl groups having 1-3 carbonatoms; andR⁴ and R⁵ are independently selected from H, F, Cl, and a linear orbranched alkyl group having 1-3 carbon atoms, optionally wherein thealkyl group comprises at least one of: fluorine, chlorine, a hydroxylgroup, or a catenated heteroatom.

Exemplary R_(f) ¹ and R_(f) ² groups include: —CF₃, —C₂F₅, —C₃F₇,—CF₂OCF₃, —CF₂OCF₃, and —CF₂OCF(CF₃)₂.

In one embodiment, R_(f) ¹ and R_(f) ² are bonded together to form a 5,6, or 7 membered ring structure. In one embodiment, R_(f) ¹ and R_(f) ²are bonded together to form a 6-membered ring comprising a catenated Oatom, forming for example a fluorinated morpholine ring. In anotherembodiment, R_(f) ¹ and R_(f) ² are bonded together in a ring structurecomprising an additional catenated nitrogen atom, wherein saidadditional nitrogen heteroatom is tertiary and is bonded to aperfluoroalkyl group having 1-3 carbon atoms. In one embodiment, R_(f) ¹and R_(f) ² are bonded together to form a 6-membered ring comprising anadditional catenated nitrogen atom, forming for example a fluorinatedpiperazine ring, wherein said additional nitrogen heteroatom is tertiaryand is bonded to a perfluoroalkyl group having 1-3 carbon atoms. In oneembodiment, R_(f) ¹ and R_(f) ² are bonded together to form apyrrolidine group.

Exemplary R_(f) ³ groups include CF₃, CF₂CF₃, CF(CF₃)₂, and (CF₂)₂CF₃.

In one embodiment, R⁴ and R⁵ are both H.

Exemplary dioxolane-containing compound of the present disclosureinclude:

In some embodiments, the dioxolane-containing compounds of the presentdisclosure may exhibit properties that render them particularly usefulas heat transfer fluids for the electronics industry. For example, thedioxolane-containing compound may be chemically inert (i.e., they do noteasily react with base, acid, water, etc.), and may have high boilingpoints (up to 300° C.), low freezing points, low viscosity, high thermalstability, good thermal conductivity, adequate solvency for a range ofpotentially important solutes, and low toxicity.

The compounds of the present disclosure have good environmentalproperties as well as having good performance attributes, such asnon-flammability, chemical inertness, high thermal stability, goodsolvency, etc.

In one embodiment, the compound of the present disclosure may have a lowenvironmental impact. In this regard, the compounds of the presentdisclosure may have a global warming potential (GWP) of less than 100,50, 40, or even 10. As used herein, GWP is a relative measure of theglobal warming potential of a compound based on the structure of thecompound. The GWP of a compound, as defined by the IntergovernmentalPanel on Climate Change (IPCC) in 1990 and updated in 2007, iscalculated as the warming due to the release of 1 kilogram of a compoundrelative to the warming due to the release of 1 kilogram of CO₂ over aspecified integration time horizon (ITH).

${{GWP}_{i}\left( t^{\prime} \right)} = {\frac{\int_{0}^{ITH}{{a_{i}\left\lbrack {C(t)} \right\rbrack}{dt}}}{\int_{0}^{ITH}{{a_{{CO}_{2}}\left\lbrack {C_{{CO}_{2}}(t)} \right\rbrack}{dt}}} = \frac{\int_{0}^{ITH}{a_{i}C_{oi}e^{{- t}/\tau_{i}}{dt}}}{\int_{0}^{ITH}{{a_{{CO}_{2}}\left\lbrack {C_{{CO}_{2}}(t)} \right\rbrack}{dt}}}}$

In this equation a_(i) is the radiative forcing per unit mass increaseof a compound in the atmosphere (the change in the flux of radiationthrough the atmosphere due to the IR absorbance of that compound), C isthe atmospheric concentration of a compound, τ is the atmosphericlifetime of a compound, t is time, and i is the compound of interest.The commonly accepted ITH is 100 years representing a compromise betweenshort-term effects (20 years) and longer-term effects (500 years orlonger). The concentration of an organic compound, i, in the atmosphereis assumed to follow pseudo first order kinetics (i.e., exponentialdecay). The concentration of CO₂ over that same time intervalincorporates a more complex model for the exchange and removal of CO₂from the atmosphere (the Bern carbon cycle model).

In one embodiment, the compounds of the present disclosure haveatmospheric lifetime of less than 1 year, 0.75 years, 0.05 years, oreven less than 0.1 years.

Non-flammability can be assessed by using standard methods such as ASTMD-3278-96 e-1, D56-05 “Standard Test Method for Flash Point of Liquidsby Small Scale Closed-Cup Apparatus”. In one embodiment, the compound ofthe present disclosure is non-flammable based on closed-cup flashpointtesting following ASTM D-327-96 e-1.

In one embodiment, the compound of the present disclosure isnon-bioaccumulative in animal tissues. For example, some compounds ofthe present disclosure may provide low log K_(ow) values, indicating areduced tendency to bioaccumulate in animal tissues, where K_(ow) is theoctanol/water partition coefficient, which is defined as the ratio ofthe given compound's concentration in a two-phase system comprising anoctanol phase and an aqueous phase. In one embodiment, the log K_(ow)value is less than 6, 5, or even 4.

In one embodiment, the compound of the present disclosure is expected toprovide low acute toxicity based on 4 hour acute inhalation or oraltoxicity studies in rats following U.S. EPA “Health Effects TestGuidelines OPPTS 870.1100 Acute Oral Toxicity” and/or OECD Test No. 436“Acute Inhalation Toxicity-Acute Toxic Class Method”. For example, acompound of the present disclosure has a single dose oral median lethaldose (LD 50) in male and female Sprague-Dawley rats of greater than 30,50, 100, 200, or even 300 mg/kg.

The useful liquid range of a compound of the present disclosure isbetween its pour point and its boiling point. A pour point is the lowesttemperature at which the compound is still able to be poured. The pourpoint can be determined, for example, by ASTM D 97-16 “Standard TestMethod for Pour Point of Petroleum Products”. In one embodiment, thecompound of the present disclosure has a pour point of less than 0° C.,−20° C., −40° C. or even −60° C. In one embodiment, the compound of thepresent disclosure has a boiling point of at least 100° C., 150° C.,200° C., 250° C. or even 300° C.

In some embodiments, the compound of the present disclosure may behydrophobic, relatively chemically unreactive, and thermally stable.

As mentioned above, the compound of the present disclosure may beprepared by a nucleophilic addition of a 1,2-diol with an ethylenicallyunsaturated compound in the presence of a suitable base to form adioxolane ring. The ethylenically unsaturated compound comprises aninternal double bond alpha to an amine and at least one olefinic C—Fbond. In one embodiment, the ethylenically unsaturated compound isperfluorinated.

The ethylenically unsaturated fluorinated compound can be prepared bystandard synthetic procedures that are well known in the art, includingthose described by Abe in JP 01070444A and JP 0107445A, which areincorporated herein by reference.

Representative examples of ethylenically unsaturated fluorinatedcompound useful as starting compounds for preparing thedioxolane-containing hydrofluoroethers of this disclosure include, forexample, 1-propenyl amines, shown in FIG. 1. Although the structures inFIG. 1 are all shown as trans isomers, the corresponding cis isomers areequally useful starting compounds. Typically the cis and transethylenically unsaturated fluorinated compounds of FIG. 1 are made andused as a mixture of cis and trans isomers.

FIG. 1: Perfluorinated 1-Propenyl Amines

Note: The 1-propenyl amines in FIG. 1, above, can be cis or transisomers or a mixture thereof, although only the trans isomers are shown.

Useful 1,2-diols are generally commercially available or readilyprepared and provide useful starting compounds for preparing thedioxolane-containing hydrofluoroether compositions of this disclosure inhigh yield. In some embodiments, hydrocarbon diols may be employed dueto their relatively lower cost (in comparison with fluorocarbon diols).In some embodiments, suitable alcohols are generally those that providedioxolane-containing compounds of the present disclosure that arenon-flammable.

Representative examples of suitable 1,2-diols include, for example,ethylene glycol, propane-1,2-diol, butane-1,2-diol,3-chloropropane-1,2-diol, 3-fluoropropane-1,2-diol, glycerol, etc.

In one embodiment, the ratio of the ethylenically unsaturatedfluorinated compound to the 1,2-diol is 1:2 to 2:1 with 1:1 typicallyused. The alcohol addition reaction illustrated in Scheme 1 can beeffected by combining the ethylenically unsaturated compound and the1,2-diol in the presence of at least one base (for example, a Lewisbase). Useful bases include potassium carbonate, cesium carbonate,potassium fluoride, potassium hydroxide, potassium methoxide,triethylamine, trimethylamine, potassium cyanate, potassium bicarbonate,sodium carbonate, sodium bicarbonate, sodium methoxide, cesium fluoride,lithium t-butoxide, potassium t-butoxide, and the like, and mixturesthereof; with potassium carbonate, potassium hydroxide, and mixturesthereof being preferred. A metal salt of the starting 1,2-diol reagentcan also be used as the base. Typically the base is present at about 2to 3 equivalents based on the ethylenically unsaturated fluorinatedcompound.

The reactants and base can be combined in a reactor (for example, aglass reactor or a metal pressure reactor) in any order, and thereaction can be run at a desired temperature with agitation. Generally,however, use of a non-reactive, aprotic organic solvent (for example,acetonitrile, acetone, tetrahydrofuran, glyme, or a mixture of two ormore thereof) can facilitate the reaction.

In one embodiment, the run temperature is from about 0° C. to about 80°C. Generally, the run temperature is above the boiling point of theethylenically unsaturated compound.

The reaction can occur at ambient or higher pressures (e.g., >760 Torr).In one embodiment the reaction is conducted in a sealed pressure vessel.In one embodiment, the reaction is exothermic so cooling of the reactionvessel can be used to maintain reaction pressure.

The reaction is run to completion (e.g., 12 hours). The reactionproduces a dioxolane-containing compound, which is typically a mixtureof various isomers.

The product can then be washed with water to remove base, salts andresidual alcohol. The recovered water layer can be washed with lowboiling nonfunctional fluorochemical to collect the fluorinated productand maximize yield. The low boiling nonfunctional fluorochemical canthen be subsequently removed to isolate the fluorinated product. In oneembodiment, the reaction yields are greater than 50, 60, 70 or even 75%.Exemplary low boiling nonfunctional fluorochemicals include thoseavailable under the trade designation “3M PERFORMANCE FLUID PF-5052”,“3M NOVEC 7100 ENGINEERED FLUID” and “3M NOVEC 7000 ENGINEERED FLUID”available from 3M Co., St. Paul, Minn.

In one embodiment, the resulting fluorinated compounds can be purifiedto isolate the desired dioxolane-containing hydrofluoro ether.Purification can be done by conventional means including distillation,absorption, extraction, chromatography and recrystallization. Thepurification can be done to isolate the compound of the presentdisclosure (in all of its stereoisomeric forms) from impurities, such asstarting materials, byproducts, etc. The term “purified form” as usedherein means the compound of the present disclosure is at least 95, 98,99%, or even 99.9 wt % pure.

The compounds of the present disclosure may be used as a working fluidin a variety of applications. The working fluids may include at least5%, 10%, 15%, 20%, 25%, 50%, 70%, 80%, 90%, 95%, 99%, or even 100% byweight of the above-described formula (I) compounds based on the totalweight of the working fluid. In addition to the compounds of the presentdisclosure, the working fluids may include a total of up to 95%, 90%,85%, 80%, 75%, up to 50%, up to 30%, up to 20%, up to 10%, or up to 5%by weight of one or more of the following components: alcohols, ethers,alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinated tertiaryamines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes,aromatics, siloxanes, unsaturated hydrochlorocarbons, unsaturatedhydrochlorofluorocarbons, unsaturated hydrofluorocarbons, non-heteroatom-containing hydrofluoroolefins, hydrochloroolefins,hydrochlorofluoroolefins, unsaturated hydrofluoroethers, or mixturesthereof, based on the total weight of the working fluid. Such additionalcomponents can be chosen to modify or enhance the properties of acomposition for a particular use.

In one embodiment, the working fluid has no flash point (as measured,for example, following ASTM D-3278-96 e-1).

In one embodiment, the compound of the present disclosure may be used inan apparatus for heat transfer that includes a device and a mechanismfor transferring heat to or from the device.

The mechanism for transferring heat may include a heat transfer workingfluid that includes a compound of formula (I) of the present disclosure.

The provided apparatus for heat transfer may include a device. Thedevice may be a component, work-piece, assembly, etc. to be cooled,heated or maintained at a predetermined temperature or temperaturerange. Such devices include electrical components, mechanical componentsand optical components. Examples of devices of the present disclosureinclude, but are not limited to microprocessors, wafers used tomanufacture semiconductor devices, power control semiconductors,electrical distribution switch gear, power transformers, circuit boards,multi-chip modules, packaged and unpackaged semiconductor devices,lasers, chemical reactors, fuel cells, and electrochemical cells. Insome embodiments, the device can include a chiller, a heater, or acombination thereof.

In yet other embodiments, the devices can include electronic devices,such as processors, including microprocessors. As these electronicdevices become more powerful, the amount of heat generated per unit timeincreases. Therefore, the mechanism of heat transfer plays an importantrole in processor performance. The heat-transfer fluid typically hasgood heat transfer performance, good electrical compatibility (even ifused in “indirect contact” applications such as those employing coldplates), as well as low toxicity, low (or non-) flammability and lowenvironmental impact. Good electrical compatibility suggests that theheat-transfer fluid candidate exhibit high dielectric strength, highvolume resistivity, and poor solvency for polar materials. Additionally,the heat-transfer fluid should exhibit good mechanical compatibility,that is, it should not affect typical materials of construction in anadverse manner.

The provided apparatus may include a mechanism for transferring heat.The mechanism may include a heat transfer fluid. The heat transfer fluidmay include one or more compounds of the present disclosure. Heat may betransferred by placing the heat transfer mechanism in thermal contactwith the device. The heat transfer mechanism, when placed in thermalcontact with the device, removes heat from the device or provides heatto the device, or maintains the device at a selected temperature ortemperature range. The direction of heat flow (from device or to device)is determined by the relative temperature difference between the deviceand the heat transfer mechanism.

The heat transfer mechanism may include facilities for managing theheat-transfer fluid, including, but not limited to pumps, valves, fluidcontainment systems, pressure control systems, condensers, heatexchangers, heat sources, heat sinks, refrigeration systems, activetemperature control systems, and passive temperature control systems.Examples of suitable heat transfer mechanisms include, but are notlimited to, temperature controlled wafer chucks in plasma enhancedchemical vapor deposition (PECVD) tools, temperature-controlled testheads for die performance testing, temperature-controlled work zoneswithin semiconductor process equipment, thermal shock test bath liquidreservoirs, and constant temperature baths. In some systems, such asetchers, ashers, PECVD chambers, vapor phase soldering devices, andthermal shock testers, the upper desired operating temperature may be ashigh as 170° C., as high as 200° C., or even as high as 230° C.

Heat can be transferred by placing the heat transfer mechanism inthermal contact with the device. The heat transfer mechanism, whenplaced in thermal contact with the device, removes heat from the deviceor provides heat to the device, or maintains the device at a selectedtemperature or temperature range. The direction of heat flow (fromdevice or to device) is determined by the relative temperaturedifference between the device and the heat transfer mechanism. Theprovided apparatus can also include refrigeration systems, coolingsystems, testing equipment and machining equipment. In some embodiments,the provided apparatus can be a constant temperature bath or a thermalshock test bath. In some systems, such as etchers, ashers, PECVDchambers, vapor phase soldering devices, and thermal shock testers, theupper desired operating temperature may be as high as 170° C., as highas 200° C., as high as 250° C. or even higher.

In some embodiments, the compounds of the present disclosure may be usedas a heat transfer agent for use in vapor phase soldering. In using thecompounds of the present disclosure in vapor phase soldering, theprocess described in, for example, U.S. Pat. No. 5,104,034 (Hansen) canbe used, which description is hereby incorporated by reference. Briefly,such process includes immersing a component to be soldered in a body ofvapor comprising at least a dioxolane-containing compound of the presentdisclosure to melt the solder, hi carrying out such a process, a liquidpool of the dioxolane-containing compound (or working fluid thatincludes the dioxolane-containing compound) is heated to boiling in atank to form a saturated vapor in the space between the boiling liquidand a condensing means,

A workpiece to be soldered is immersed in the vapor (at a temperature ofgreater than 170° C., greater than 200° C., greater than 230° C., 250C,or even greater), whereby the vapor is condensed on the surface of theworkpiece so as to melt and reflow the solder. Finally, the solderedworkpiece is then removed from the space containing the vapor.

In another embodiment, the compound of the present disclosure is used inan apparatus for converting thermal energy into mechanical energy in aRankine cycle. The apparatus may include a working fluid that includesone or more compounds of formula (I). The apparatus may further includea heat source to vaporize the working fluid and form a vaporized workingfluid, a turbine through which the vaporized working fluid is passedthereby converting thermal energy into mechanical energy, a condenser tocool the vaporized working fluid after it is passed through the turbine,and a pump to recirculate the working fluid.

In some embodiments, the present disclosure relates to a process forconverting thermal energy into mechanical energy in a Rankine cycle. Theprocess may include using a heat source to vaporize a working fluid thatincludes one or more compounds of formula (I) to form a vaporizedworking fluid. In some embodiments, the heat is transferred from theheat source to the working fluid in an evaporator or boiler. Thevaporized working fluid may be pressurized and can be used to do work byexpansion. The heat source can be of any form such as from fossil fuels,e.g., oil, coal, or natural gas. Additionally, in some embodiments, theheat source can come from nuclear power, solar power, or fuel cells. Inother embodiments, the heat can be “waste heat” from other heat transfersystems that would otherwise be lost to the atmosphere. The “wasteheat,” in some embodiments, can be heat that is recovered from a secondRankine cycle system from the condenser or other cooling device in thesecond Rankine cycle.

An additional source of “waste heat” can be found at landfills wheremethane gas is flared off. In order to prevent methane gas from enteringthe environment and thus contributing to global warming, the methane gasgenerated by the landfills can be burned by way of “flares” producingcarbon dioxide and water which are both less harmful to the environmentin terms of global warming potential than methane. Other sources of“waste heat” that can be useful in the provided processes are geothermalsources and heat from other types of engines such as gas turbine enginesthat give off significant heat in their exhaust gases and to coolingliquids such as water and lubricants.

In the provided process, the vaporized working fluid may expanded thougha device that can convert the pressurized working fluid into mechanicalenergy. In some embodiments, the vaporized working fluid is expandedthrough a turbine which can cause a shaft to rotate from the pressure ofthe vaporized working fluid expanding. The turbine can then be used todo mechanical work such as, in some embodiments, operate a generator,thus generating electricity. In other embodiments, the turbine can beused to drive belts, wheels, gears, or other devices that can transfermechanical work or energy for use in attached or linked devices.

After the vaporized working fluid has been converted to mechanicalenergy the vaporized (and now expanded) working fluid can be condensedusing a cooling source to liquefy for reuse. The heat released by thecondenser can be used for other purposes including being recycled intothe same or another Rankine cycle system, thus saving energy. Finally,the condensed working fluid can be pumped by way of a pump back into theboiler or evaporator for reuse in a closed system.

The desired thermodynamic characteristics of organic Rankine cycleworking fluids are well known to those of ordinary skill and arediscussed, for example, in U.S. Pat. Appl. Publ. No. 2010/0139274(Zyhowski et al.). The greater the difference between the temperature ofthe heat source and the temperature of the condensed liquid or aprovided heat sink after condensation, the higher the Rankine cyclethermodynamic efficiency. The thermodynamic efficiency is influenced bymatching the working fluid to the heat source temperature. The closerthe evaporating temperature of the working fluid to the sourcetemperature, the higher the efficiency of the system. Toluene can beused, for example, in the temperature range of 79° C. to about 260° C.,however toluene has toxicological and flammability concerns. Fluids suchas 1,1-dichloro-2,2,2-trifluoroethane and 1,1,1,3,3-pentafluoropropanecan be used in this temperature range as an alternative. But1,1-dichloro-2,2,2-trifluoroethane can form toxic compounds below 300°C. and need to be limited to an evaporating temperature of about 93° C.to about 121° C. Thus, there is a desire for otherenvironmentally-friendly Rankine cycle working fluids with highercritical temperatures so that source temperatures such as gas turbineand internal combustion engine exhaust can be better matched to theworking fluid.

in one embodiment, the compound of the present disclosure is used in acleaning composition along with one or more co-solvents. In someembodiments, the present disclosure relates to a process for cleaning asubstrate. The cleaning process can be carried out by contacting acontaminated substrate with a cleaning composition. The compound of thepresent disclosure can be utilized alone or in admixture with each otheror with other commonly-used cleaning co-solvents. Representativeexamples of co-solvents which can be used in the cleaning compositioninclude methanol, ethanol, isopropanol, t-butyl alcohol, methyl t-butylether, methyl t-amyl ether, 1,2-dimethoxyethane, cyclohexane,2,2,4-trimethylpentane, n-decane, terpenes (e.g., a-pinene, camphene,and limonene), trans-1,2-dichloroethylene, cis-1,2-dichloroethylene,methylcyclopentane, decalin, methyl decanoate, t-butyl acetate, ethylacetate, diethyl phthalate, 2-butanone, methyl isobutyl ketone,naphthalene, toluene, p-chlorobenzotrifluoride, trifluorotoluene,bis(trifluoromethyl)benzenes, hexamethyl disiloxane, octamethyltrisiloxane, perfluorohexane, perfluoroheptane, perfluorooctane,perfluorotributylamine, perfluoro-N-methyl morpholine, perfluoro-2-butyloxacyclopentane, methylene chloride, chlorocyclohexane, 1-chlorobutane,1,1-dichloro-1-fluoroethane, 1,1,1-trifluoro-2,2-dichloroethane,1,1,1,2,2-pentafluoro-3,3-dichloropropane,1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,3-dihydroperfluoropentane,1,1,1,2,2,4-hexafluorobutane,1-trifluoromethyl-1,2,2-trifluorocyclobutane,3-methyl-1,1,2,2-tetrafluorocyclobutane, 1-hydropentadecafluoroheptane,or mixtures thereof. Such co-solvents can be chosen to modify or enhancethe solvency properties of a cleaning composition for a particular useand can be utilized in ratios (of co-solvent to compounds according toformula (I)) such that the resulting composition has no flash point. Ifdesirable for a particular application, the cleaning composition canfurther contain one or more dissolved or dispersed gaseous, liquid, orsolid additives (for example, carbon dioxide gas, surfactants,stabilizers, antioxidants, or activated carbon).

In some embodiments, the present disclosure relates to cleaningcompositions that include one or more compounds of the presentdisclosure and optionally one or more surfactants. Suitable surfactantsinclude those surfactants that are sufficiently soluble in the compoundof the present disclosure, and which promote soil removal by dissolving,dispersing or displacing the soil. One useful class of surfactants arethose nonionic surfactants that have a hydrophilic-lipophilic balance(HLB) value of less than about 14. Examples include ethoxylatedalcohols, ethoxylated alkylphenols, ethoxylated fatty acids, alkylarylsulfonates, glycerol esters, ethoxylated fluoroalcohols, and fluorinatedsulfonamides. Mixtures of surfactants having complementary propertiesmay be used in which one surfactant is added to the cleaning compositionto promote oily soil removal and another added to promote water-solublesoil removal. The surfactant, if used, can be added in an amountsufficient to promote soil removal. Typically, surfactant may be addedin amounts from 0.1 to 5.0 wt. % or from 0.2 to 2.0 wt. % of thecleaning composition.

The cleaning compositions can be used in either the gaseous or theliquid state (or both), and any of known or future techniques for“contacting” a substrate can be utilized. For example, a liquid cleaningcomposition can be sprayed or brushed onto the substrate, a gaseouscleaning composition can be blown across the substrate, or the substratecan be immersed in either a gaseous or a liquid composition. Elevatedtemperatures, ultrasonic energy, and/or agitation can be used tofacilitate the cleaning. Various different solvent cleaning techniquesare described by B. N. Ellis in Cleaning and Contamination ofElectronics Components and Assemblies, Electrochemical PublicationsLimited, Ayr, Scotland, pages 182-94 (1986).

Both organic and inorganic substrates can be cleaned by the processes ofthe present disclosure. Representative examples of the substratesinclude metals; ceramics; glass; polycarbonate; polystyrene;acrylonitrile-butadiene-styrene copolymer; natural fibers (and fabricsderived therefrom) such as cotton, silk, fur, suede, leather, linen, andwool; synthetic fibers (and fabrics) such as polyester, rayon, acrylics,nylon, or blends thereof; fabrics comprising a blend of natural andsynthetic fibers; and composites of the foregoing materials. In someembodiments, the process may be used in the precision cleaning ofelectronic components (e.g., circuit boards), optical or magnetic media,or medical devices.

In still another embodiment, the compound of the present disclosure isused in a dielectric fluids, which can be used in electrical devices(e.g., capacitors, switchgear, transformers, or electric cables orbuses). For purposes of the present application, the term “dielectricfluid” is inclusive of both liquid dielectrics and gaseous dielectrics.The physical state of the fluid, gaseous or liquid, is determined at theoperating conditions of temperature and pressure of the electricaldevice in which it is used.

In some embodiments, the dielectric fluids include one or more compoundsof formula (I) and, optionally, one or more second dielectric fluids.Suitable second dielectric fluids include, for example, air, nitrogen,helium, argon, and carbon dioxide, or combinations thereof. The seconddielectric fluid may be a non-condensable gas or an inert gas.Generally, the second dielectric fluid may be used in amounts such thatvapor pressure is at least 70 kPa at 25° C., or at the operatingtemperature of the electrical device.

The dielectric fluids of the present application comprising thecompounds of formula (I) are useful for electrical insulation and forarc quenching and current interruption equipment used in thetransmission and distribution of electrical energy. Generally, there arethree major types of electrical devices in which the fluids of thepresent disclosure can be used: (1) gas-insulated circuit breakers andcurrent-interruption equipment, (2) gas-insulated transmission lines,and (3) gas-insulated transformers. Such gas-insulated equipment is amajor component of power transmission and distribution systems.

In some embodiments, the present disclosure provides electrical devices,such as capacitors, comprising metal electrodes spaced from each othersuch that the gaseous dielectric fills the space between the electrodes.The interior space of the electrical device may also comprise areservoir of the liquid dielectric fluid which is in equilibrium withthe gaseous dielectric fluid. Thus, the reservoir may replenish anylosses of the dielectric fluid.

In another embodiment, the present disclosure relates to coatingcompositions comprising (a) a solvent composition that includes one ormore compounds of the present disclosure, and (b) one or more coatingmaterials which are soluble or dispersible in the solvent composition.

In various embodiments, the coating materials of the coatingcompositions may include pigments, lubricants, stabilizers, adhesives,anti-oxidants, dyes, polymers, pharmaceuticals, release agents,inorganic oxides, and the like, and combinations thereof. For example,coating materials may include unsaturated perfluoropolyether,unsaturated hydrocarbon, and silicone lubricants; amorphous copolymersof tetrafluoroethylene; polytetrafluoroethylene; or combinationsthereof. Further examples of suitable coating materials include titaniumdioxide, iron oxides, magnesium oxide, unsaturated perfluoropolyethers,polysiloxanes, stearic acid, acrylic adhesives, polytetrafluoroethylene,amorphous copolymers of tetrafluoroethylene, or combinations thereof.

In some embodiments, the above-described coating compositions can beuseful in coating deposition, where the compounds of formula (I)function as a carrier for a coating material to enable deposition of thematerial on the surface of a substrate. In this regard, the presentdisclosure further relates to a process for depositing a coating on asubstrate surface using the coating composition. The process comprisesthe step of applying to at least a portion of at least one surface of asubstrate a coating of a liquid coating composition comprising (a) asolvent composition containing one or more of the compounds of formula(I); and (b) one or more coating materials which are soluble ordispersible in the solvent composition. The solvent composition canfurther comprise one or more co-dispersants or co-solvents and/or one ormore additives (e.g., surfactants, coloring agents, stabilizers,anti-oxidants, flame retardants, and the like). Preferably, the processfurther comprises the step of removing the solvent composition from thecoating by, e.g., allowing evaporation (which can be aided by theapplication of, e.g., heat or vacuum).

In various embodiments, to form a coating composition, the components ofthe coating composition (i.e., the compound(s) of formula (I), thecoating material(s), and any co-dispersant(s) or co-solvent(s) utilized)can be combined by any conventional mixing technique used fordissolving, dispersing, or emulsifying coating materials, e.g., bymechanical agitation, ultrasonic agitation, manual agitation, and thelike. The solvent composition and the coating material(s) can becombined in any ratio depending upon the desired thickness of thecoating. For example, the coating material(s) may constitute from about0.1 to about 10 weight percent of the coating composition.

In illustrative embodiments, the deposition process of the disclosurecan be carried out by applying the coating composition to a substrate byany conventional technique. For example, the composition can be brushedor sprayed (e.g., as an aerosol) onto the substrate, or the substratecan be spin-coated. In some embodiments, the substrate may be coated byimmersion in the composition. Immersion can be carried out at anysuitable temperature and can be maintained for any convenient length oftime. If the substrate is a tubing, such as a catheter, and it isdesired to ensure that the composition coats the lumen wall, thecomposition may be drawn into the lumen by the application of reducedpressure.

In various embodiments, after a coating is applied to a substrate, thesolvent composition can be removed from the coating (e.g., byevaporation). If desired, the rate of evaporation can be accelerated byapplication of reduced pressure or mild heat. The coating can be of anyconvenient thickness, and, in practice, the thickness will be determinedby such factors as the viscosity of the coating material, thetemperature at which the coating is applied, and the rate of withdrawal(if immersion is utilized).

Both organic and inorganic substrates can be coated by the processes ofthe present disclosure. Representative examples of the substratesinclude metals, ceramics, glass, polycarbonate, polystyrene,acrylonitrile-butadiene-styrene copolymer, natural fibers (and fabricsderived therefrom) such as cotton, silk, fur, suede, leather, linen, andwool, synthetic fibers (and fabrics) such as polyester, rayon, acrylics,nylon, or blends thereof, fabrics including a blend of natural andsynthetic fibers, and composites of the foregoing materials. In someembodiments, substrates that may be coated include, for example,magnetic hard disks or electrical connectors with perfluoropolyetherlubricants or medical devices with silicone lubricants.

In some embodiments, the present disclosure further relates toelectrolyte compositions that include one or more compounds of thepresent disclosure. The electrolyte compositions may comprise (a) asolvent composition including one or more of the compounds according toformula (I); and (b) at least one electrolyte salt. The electrolytecompositions of the present disclosure exhibit excellent oxidativestability, and when used in high voltage electrochemical cells (such asrechargeable lithium ion batteries) provide outstanding cycle life andcalendar life. For example, when such electrolyte compositions are usedin an electrochemical cell with a graphitized carbon electrode, theelectrolytes provide stable cycling to a maximum charge voltage of atleast 4.5V and up to 6.0V vs. Li/Li⁺.

Electrolyte salts that are suitable for use in preparing the electrolytecompositions of the present disclosure include those salts that compriseat least one cation and at least one weakly coordinating anion (theconjugate acid of the anion having an acidity greater than or equal tothat of a hydrocarbon sulfonic acid (for example, PF₆ ⁻ anion or abis(perfluoroalkanesulfonyl)imide anion); that are at least partiallysoluble in a selected compound of formula (I) (or in a blend thereofwith one or more other compounds of formula (I) or one or moreconventional electrolyte solvents); and that at least partiallydissociate to form a conductive electrolyte composition. The salts maybe stable over a range of operating voltages, are non-corrosive, and maybe thermally and hydrolytically stable. Suitable cations include alkalimetal, alkaline earth metal, Group IIB metal, Group IIIB metal,transition metal, rare earth metal, and ammonium (for example,tetraalkylammonium or trialkylammonium) cations, as well as a proton. Insome embodiments, cations for battery use include alkali metal andalkaline earth metal cations. Suitable anions includefluorine-containing inorganic anions such as (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻,AsF₆ ⁻, and SbF₆ ⁻; CIO₄ ⁻; HSO₄ ⁻; H₂PO₄ ⁻; organic anions such asalkane, aryl, and alkaryl sulfonates; fluorine-containing andnonfluorinated tetraarylborates; carboranes and halogen-, alkyl-, orhaloalkylsubstituted carborane anions including metallocarborane anions;and fluorine-containing organic anions such asperfluoroalkanesulfonates, cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,(perfluoroalkanesulfonypimides, bis(perfluoroalkanesulfonyl)methides,and tris(perfluoroalkanesulfonyl)methides; and the like. Preferredanions for battery use include fluorine-containing inorganic anions (forexample, (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻, and AsF₆ ⁻) and fluorine-containingorganic anions (for example, perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides). The fluorine-containing organicanions can be either fully fluorinated, that is perfluorinated, orpartially fluorinated (within the organic portion thereof). In someembodiments, the fluorine-containing organic anion is at least about 80percent fluorinated (that is, at least about 80 percent of thecarbon-bonded substituents of the anion are fluorine atoms). In someembodiments, the anion is perfluorinated. The anions, including theperfluorinated anions, can contain one or more catenary heteroatoms suchas, for example, nitrogen, oxygen, or sulfur. In some embodiments,fluorine-containing organic anions include perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides.

In some embodiments, the electrolyte salts may include lithium salts.Suitable lithium salts include, for example, lithiumhexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithiumbis(perfluoroethanesulfonyl)imide, lithium tetrafluoroborate, lithiumperchlorate, lithium hexafluoroarsenate, lithiumtrifluoromethanesulfonate, lithiumtris(trifluoromethanesulfonyl)methide, lithium bis(fluorosulfonyl)imide(Li-FSI), and mixtures of two or more thereof.

The electrolyte compositions of the present disclosure can be preparedby combining at least one electrolyte salt and a solvent compositionincluding at least one compound of formula (I), such that the salt is atleast partially dissolved in the solvent composition at the desiredoperating temperature. The compounds of the present disclosure (or anormally liquid composition including, consisting, or consistingessentially thereof) can be used in such preparation.

In some embodiments, the electrolyte salt is employed in the electrolytecomposition at a concentration such that the conductivity of theelectrolyte composition is at or near its maximum value (typically, forexample, at a Li molar concentration of around 0.1-4.0 M, or 1.0-2.0 M,for electrolytes for lithium batteries), although a wide range of otherconcentrations may also be employed.

In some embodiments, one or more conventional electrolyte solvents aremixed with the compound(s) of formula (I) (for example, such that thecompound(s) of formula (I) constitute from about 1 to about 80 or 90percent of the resulting solvent composition). Useful conventionalelectrolyte solvents include, for example, organic andfluorine-containing electrolyte solvents (for example, propylenecarbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate,ethyl methyl carbonate, dimethoxyethane, 7-butyrolactone, diglyme (thatis, diethylene glycol dimethyl ether), tetraglyme (that is,tetraethylene glycol dimethyl ether), monofluoroethylene carbonate,vinylene carbonate, ethyl acetate, methyl butyrate, tetrahydrofuran,alkyl-substituted tetrahydrofuran, 1,3-dioxolane, alkyl-substituted1,3-dioxolane, tetrahydropyran, alkyl-substituted tetrahydropyran, andthe like, and mixtures thereof). Other conventional electrolyteadditives (for example, a surfactant) can also be present, if desired.

The present disclosure further relates to electrochemical cells (e.g.,fuel cells, batteries, capacitors, electrochromic windows) that includethe above-described electrolyte compositions. Such an electrochemicalcell may include a positive electrode, a negative electrode, aseparator, and the above-described electrolyte composition.

A variety of negative and positive electrodes may be employed in theelectrochemical cells. Representative negative electrodes includegraphitic carbons e.g., those having a spacing between (002)crystallographic planes, d₀₀₂, of 3.45 A>d₀₀₂>3.354 A and existing informs such as powders, flakes, fibers or spheres (e.g., mesocarbonmicrobeads); Li_(4/3)Ti_(5/3)O₄ the lithium alloy compositions describedin U.S. Pat. No. 6,203,944 (Turner et al.) and U.S. Pat. No. 6,255,017(Turner); and combinations thereof. Representative positive electrodesinclude LiFePO₄, LiMnPO₄, LiCoPO₄, LiMn₂O₄, LiCoO₂ and combinationsthereof. The negative or positive electrode may contain additives suchas will be familiar to those skilled in the art, e.g., carbon black fornegative electrodes and carbon black, flake graphite and the like forpositive electrodes.

The electrochemical devices of the present disclosure can be used invarious electronic articles such as computers, power tools, automobiles,telecommunication devices, and the like.

Exemplary embodiments of the present disclosure, include, but are notlimited to the following:

Embodiment 1

A dioxolane-containing compound of formula (I)

wherein (i) R_(f) ¹ and R_(f) ² are independently linear or branchedperfluoroalkyl groups having with 1-8 carbon atoms and optionallycomprise at least one catenated heteroatom, or (ii) R_(f) ¹ and R_(f) ²are bonded together to form a ring structure having 4-6 carbon atoms andoptionally comprise one or more catenated heteroatoms;R_(f) ³ is a linear or branched perfluoroalkyl groups having with 1-3carbon atoms; andR⁴ and R⁵ are independently selected from H, F, Cl, a linear or branchedalkyl group having 1-3 carbon atoms, optionally wherein the alkyl groupcomprises at least one of: fluorine, chlorine, a hydroxyl group, or acatenated heteroatom.

Embodiment 2

The dioxolane-containing compound of embodiment 1, wherein R⁴ and R⁵ areH.

Embodiment 3

The dioxolane-containing compound of any one of the previousembodiments, wherein R_(f) ³ is CF₃.

Embodiment 4

The dioxolane-containing compound of any one of the previousembodiments, wherein R_(f) ¹ and R_(f) ² are bonded together to form a5, 6, or 7 membered ring.

Embodiment 5

The dioxolane-containing compound of any one of the previousembodiments, wherein R_(f) ¹ and R_(f) ³ are bonded together to form a6-membered perfluorinated ring comprising a catenated O atom.

Embodiment 6

The dioxolane-containing compound of embodiment 5, wherein R_(f) ¹ andR_(f) ² form a morpholine group.

Embodiment 7

The dioxolane-containing compound of any one embodiments 1-4, whereinR_(f) ¹ and R_(f) ² are bonded together to form a 6-memberedperfluorinated ring comprising an additional catenated N atom.

Embodiment 8

The dioxolane-containing compound of embodiment 7, wherein R_(f) ¹ andR_(f) ² form an N-perfluoroalkyl piperizine group.

Embodiment 9

The dioxolane-containing compound of any one of embodiments 1-4, whereinR_(f) ¹ and R_(f) ² form a pyrrolidine group.

Embodiment 10

The dioxolane-containing compound of any one of embodiments 1-3, whereinR_(f) ¹ and R_(f) ² are independently selected from CF₃, C₂F₅, and C₃F₇.

Embodiment 11

The dioxolane-containing compound of any one of the previousembodiments, wherein the dioxolane-containing compound is nonflammablebased on closed-cup flashpoint testing following ASTM D-327-96 e-1.

Embodiment 12

The dioxolane-containing compound of any one of the previousembodiments, wherein the dioxolane-containing compound has a globalwarming potential of less than 100.

Embodiment 13

A composition comprising a purified form of the dioxolane-containingcompound according to any one of the previous embodiments.

Embodiment 14

A working fluid comprising the dioxolane-containing compound accordingto any one of embodiments 1-11, wherein the dioxolane-containingcompound is present in the working fluid in an amount of at least 5% byweight based on the total weight of the working fluid.

Embodiment 15

The working fluid of embodiment 14, wherein the working fluid furthercomprises a co-solvent.

Embodiment 16

Use of the dioxolane-containing compound of any one embodiments 1-11,wherein the dioxolane-containing compound is in a cleaning composition.

Embodiment 17

Use of the dioxolane-containing compound of any one embodiments 1-11,wherein the dioxolane-containing compound is an electrolyte solvent oradditive.

Embodiment 18

Use of the dioxolane-containing compound of any one embodiments 1-11,wherein the dioxolane-containing compound is a heat transfer fluid.

Embodiment 19

Use of the dioxolane-containing compound of any one embodiments 1-11,wherein the dioxolane-containing compound is a vapor phase solderingfluid.

Embodiment 20

An apparatus for heat transfer comprising:

a device; and

a mechanism for transferring heat to or from the device, the mechanismcomprising a heat transfer fluid that comprises the dioxolane-containingcompound according to any one of embodiments 1-11.

Embodiment 21

An apparatus for heat transfer according to embodiment 20, wherein thedevice is selected from a microprocessor, a semiconductor wafer used tomanufacture a semiconductor device, a power control semiconductor, anelectrochemical cell, an electrical distribution switch gear, a powertransformer, a circuit board, a multi-chip module, a packaged orunpackaged semiconductor device, a fuel cell, and a laser.

Embodiment 22

An apparatus according to any one of embodiments 20-21, wherein themechanism for transferring heat is a component in a system formaintaining a temperature or temperature range of an electronic device.

Embodiment 23

An apparatus according to any one of embodiments 20-21, wherein thedevice comprises an electronic component to be soldered.

Embodiment 24

A method of transferring heat comprising:

providing a device; and

transferring heat to or from the device using a heat transfer fluid thatcomprises a dioxolane-containing compound according to any one ofembodiments 1-11.

Embodiment 25

A method of making the dioxolane-containing hydrofluoroether, the methodcomprising:

(a) contacting a 1,2-diol compound with a fluorinated ethylenicallyunsaturated compound in the presence of a base, the fluorinatedethylenically unsaturated compound comprising (i) an internal doublebond, (ii) an olefinic C—F bond, and (iii) a fluorine atom alpha to theinternal double bond.

EXAMPLES

Unless otherwise noted, all parts, percentages, ratios, etc. in theexamples and the rest of the specification are by weight, and allreagents used in the examples were obtained, or are available, fromgeneral chemical suppliers such as, for example, Sigma-Aldrich Company,Saint Louis, Mo., or may be synthesized by conventional methods.

These abbreviations are used in the following examples: phr=parts perhundred rubber; g=grams, min=minutes, h=hour, ° C.=degrees Celsius,MPa=megapascals, and N-m=Newton-meter.

Example 1: Preparation of

Ethylene glycol (36 g, 5.81.62 mmol, 1.5 equiv.), potassium hydroxide(43.51 g, 775.49 mmol, 2 equiv.), and acetonitrile (140 g) were added toa stainless steel Parr reactor (obtained from Parr Instrument Company,Moline Ill.). The apparatus was sealed and cooled to −78° C. The reactorwas evacuated and2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1-en-1-yl)morpholine (140 g,387.74 mmol, 1 equiv.) was vacuum transferred to the apparatus. Thevessel was fully sealed and allowed to reach room temperature and wassubsequently heated to 80° C. for 72 h. The reactor was then cooled andvented. The contents were poured into a 1 L beaker containing ice water.The fluorochemical phase was collected and the water layer was washed(3×, 100 mL each time) with a fully-fluorinated liquid (available underthe trade designation “3M PERFORMANCE LIQUID PF-5052”, from 3M Co., St.Paul, Minn.). The fluorochemical phases were collected and the materialwas purified via fractional distillation to afford2,2,3,3,5,5,6,6-octafluoro-4-(fluoro(2-(trifluoromethyl)-1,3-dioxolan-2-yl)methyl)morpholineas a clear, colorless liquid.

Example 2: Preparation of

Ethylene glycol (51.1 mL, 914 mmol), potassium hydroxide (126 g, 1826.6mmol, 2.2 equiv.), and acetonitrile (117 g) were added to a stainlesssteel Parr reactor (obtained from Parr Instrument Company, Moline Ill.).The apparatus was sealed and cooled down to −78° C. The reactor wasevacuated and1,2,3,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine (235 g,830.27 mmol) was vacuum transferred to the apparatus. The vessel wasfully sealed and allowed to reach room temperature and was subsequentlyheated to 80° C. for 72 h. The reactor was then cooled and vented. Thecontents were poured into a 1 L beaker containing ice water. Thefluorochemical phase was collected and the water layer was washed (3×,100 mL each time) with a fully-fluorinated liquid (available under thetrade designation “3M PERFORMANCE LIQUID PF-5052”, from 3M Co., St.Paul, Minn.). The fluorochemical phases were collected and the materialwas purified via fractional distillation to afford1,1,1-trifluoro-N-[fluoro-[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methyl]-N-(trifluoromethyl)methanamine(155 g, 57% yield) as a clear, colorless liquid.

What is claimed is:
 1. A dioxolane-containing compound of formula (I)

wherein (i) R_(f) ¹ and R_(f) ² are independently linear or branchedperfluoroalkyl groups having with 1-8 carbon atoms and optionallycomprise at least one catenated heteroatom, or (ii) R_(f) ¹ and R_(f) ²are bonded together to form a ring structure having 4-6 carbon atoms andoptionally comprise one or more catenated heteroatoms; R_(f) ³ is alinear or branched perfluoroalkyl groups having with 1-3 carbon atoms;and R⁴ and R⁵ are independently selected from H, F, Cl, a linear orbranched alkyl group having 1-3 carbon atoms, optionally wherein thealkyl group comprises at least one of: fluorine, chlorine, a hydroxylgroup, or a catenated heteroatom.
 2. The dioxolane-containing compoundof claim 1, wherein R⁴ and R⁵ are H.
 3. The dioxolane-containingcompound of claim 1, wherein R_(f) ³ is CF₃.
 4. The dioxolane-containingcompound of claim 1, wherein R_(f) ¹ and R_(f) ² are bonded together toform a 5, 6, or 7 membered ring.
 5. The dioxolane-containing compound ofclaim 1, wherein R_(f) ¹ and R_(f) ² are bonded together to form a6-membered perfluorinated ring comprising a catenated 0 atom.
 6. Thedioxolane-containing compound of claim 5, wherein R_(f) ¹ and R_(f) ²form a morpholine group.
 7. The dioxolane-containing compound of claim1, wherein R_(f) ¹ and R_(f) ² are bonded together to form a 6-memberedperfluorinated ring comprising an additional catenated N atom.
 8. Thedioxolane-containing compound of claim 7, wherein R_(f) ¹ and R_(f) ²form an N-perfluoroalkyl piperizine group.
 9. The dioxolane-containingcompound of claim 1, wherein R_(f) ¹ and R_(f) ² form a pyrrolidinegroup.
 10. The dioxolane-containing compound of claim 1, wherein R_(f) ¹and R_(f) ² are independently selected from CF₃, C₂F₅, and C₃F₇.
 11. Aworking fluid comprising the dioxolane-containing compound according toclaim 1, wherein the dioxolane-containing compound is present in theworking fluid in an amount of at least 5% by weight based on the totalweight of the working fluid.
 12. An apparatus for heat transfercomprising: a device; and a mechanism for transferring heat to or fromthe device, the mechanism comprising a heat transfer fluid thatcomprises the dioxolane-containing compound according to claim
 1. 13. Amethod of transferring heat comprising: providing a device; andtransferring heat to or from the device using a heat transfer fluid thatcomprises a dioxolane-containing compound according to claim
 1. 14. Acomposition comprising a purified form of the dioxolane-containingcompound according to claim
 1. 15. The dioxolane-containing compound ofclaim 1, wherein the dioxolane-containing compound is nonflammable basedon closed-cup flashpoint testing following ASTM D-327-96 e-1.
 16. Thedioxolane-containing compound of claim 1, wherein thedioxolane-containing compound has a global warming potential of lessthan
 100. 17. The working fluid of claim 11, wherein the working fluidfurther comprises a co-solvent.
 18. An apparatus according to claim 12,wherein the mechanism for transferring heat is a component in a systemfor maintaining a temperature or temperature range of an electronicdevice.